Probing organization and communication at layered interfaces

We have investigated the local organization intrinsic to a variety of interfacial structures, by both electrochemical and spectroscopic means. Our focus has been on the design and construction of biomimetic interfaces, where a lipid bilayer or a hybrid bilayer membrane can be bound to an interface. The goal of this work is ultimately to create an interface on a transducer surface that can support an enzyme in its active form. To this point, we have examined the extent of organization that is achievable in monolayers that will be used to bind bilayer structures to a transducer surface. Our electrochemical data point to the important role of the substrate surface in determining adlayer organization. We have also investigated the fluidity and structural heterogeneity of lipid bilayers using time-resolved and steady state fluorescence spectroscopy. Our data point to the highly interactive nature of lipid bilayer constituents, where perturbations introduced to one region have significant consequences on other regions of the bilayer. Such information is directly relevant to the existence and properties of lipid raft structures in both model and biological bilayers.     

Amphiphilic derivatives of dextran: adsorption at air/water and oil/water interfaces

Ionic amphiphilic dextran derivatives were synthesized by the attachment of sodium sulfopropyl and phenoxy groups on the native polysaccharide. A family of dextran derivatives was thus obtained with varying hydrophobic content and charge density in the polymer chains. The surface-active properties of polymers were studied at the air-water and dodecane-water interfaces using dynamic surface/interfacial tension measurements. The adsorption was shown to begin in a diffusion-limited regime at low polymer concentrations, that is to say, with the diffusion of macromolecules in the bulk solution. In contrast, at long times the interfacial adsorption is limited by interfacial phenomena: adsorption kinetics or transfer into the adsorbed layer. A semiempirical equation developed by Filippov was shown to correctly fit the experimental curves over the whole time range. The presence of ionic groups in the chains strongly lowers the adsorption kinetics. This effect can be interpreted by electrostatic interactions between the free molecules and the already adsorbed ones. The adsorption kinetics at air-water and oil-water interfaces are compared.     

A two-state solvent model for rigid rods adsorption at charged interfaces

A simple two-state solvent model is developed to describe the adsorption of rigid rods at polarizable interfaces. The adsorption isotherm and the equation of state are determined by means of the lattice theory of strictly regular solutions, assuming that the solvent at the interface exists in the form of monomers with two possible orientations, and the adsorbed rods are oriented normal to the electrode surface. In the case of the mercury/aqueous inert electrolyte interface in the presence of small, polar, aliphatic hydrocarbon derivatives, the model predicts that the variation of the isotherm interaction parameter is determined mainly by the dipole-dipole interactions between the permanent dipoles of the adsorbed molecules. This variation becomes more pronounced as the dipolar interactions between adsorbate-solvent molecules become more intense. The Marshall-Conway treatment for the polarization catastrophe and the approach of Levine et al. in incorporating polarizability effects are also taken into consideration and examined critically.     

Mobility and in situ aggregation of charged microparticles at oil-water interfaces

Particle mobility, aggregate structure, and the mechanism of aggregate growth at the two-dimensional level have been of long-standing interest. Here, we use solid-stabilized emulsions as a model system to investigate the mobility of charged microparticles at poly(dimethylsiloxane) (oil)-water interfaces using confocal laser scanning microscopy. Remarkably, the rate of diffusion of the charged colloidal-sized polystyrene particles at the oil-water interface is only moderately slower than that in the bulk water phase. The ambient diffusion constant of solid particles is significantly reduced from 1.1 x 10(-9) cm2/s to 2.1 x 10(-11) cm2/s when the viscosity of the oil phase increases from 5 cSt to 350 cSt. In addition, we successfully observe the in situ structural formation of solid particles at the oil-water interface.     

Adsorption/aggregation of surfactants and their mixtures at solid-liquid interfaces

Adsorption of surfactants and polymers at solid-liquid interfaces is used widely to modify interfacial properties in a variety of industrial processes such as flotation, ceramic processing, flocculation/dispersion, personal care product formulation and enhanced oil recovery. The behavior of surfactants and polymers at interfaces is determined by a number of forces, including electrostatic attraction, covalent bonding, hydrogen bonding, hydrophobic bonding, and solvation and desolvation of various species. The extent and type of the forces involved varies depending on the adsorbate and the adsorbent, and also the composition and other characteristics of the solvent and dissolved components in it. The influence of such forces on the adsorption behavior is reviewed here from a thermodynamics point of view. The experimental results from microcalorimetric and spectroscopic studies of adsorbed layers of different surfactant and polymer systems at solid-liquid interfaces are also presented. Calorimetric data from the adsorption of an anionic surfactant, sodium octylbenzenesulfonate, and a non-ionic surfactant, dodecyloxyheptaethoxyethylalcohol, and their mixtures on alumina, yielded important thermodynamic information. It was found that the adsorption of anionic surfactants alone on alumina was initially highly exothermic due to the electrostatic interaction with the substrate. Further adsorption leading to a solloid (hemimicelle) formation is proposed to be mainly an entropy-driven process. The entropy effect was found to be more pronounced for the adsorption of anionic-non-ionic surfactant mixtures than for the anionic surfactant alone. Fluorescence studies using a pyrene probe on an adsorbed surfactant and polymer layers, along with electron spin resonance (ESR) spectroscopy, reveal the role of surface aggregation and the conformation of the adsorbed molecules in controlling the dispersion and wettability of the system.     

Eccentric phenomena at liquid mercury electrode/solution interfaces: upward, downward, and circular motions

The present paper describes a visualization of unidirectional and circular motions triggered by an electrochemical redox reaction at a charged, bent, and streamed liquid electrode/liquid solution interface. The novel circular motion that induces a conversion of electrochemical energy into mechanical energy could be visualized for the first time at a hanging mercury drop electrode (HMDE)/dimethyl sulfoxide (DMSO) solution interface via the electrochromic reaction of 2,1,3-benzothiadiazole (BTD) by using a CCD-color video camera. The observed motions are self-insisting in nature and are tunable into upward, downward, clockwise, and anticlockwise ones by an appropriate choice of the experimental conditions. This circular motion is visualized for the first time as the cause of the well-known cyclic voltammetric anodic current oscillation at the HMDE. Several small perturbations, for example, surface tension, surface motion, bulk motion, diffusional mass transport, and surface electrochemical potential are considered to be endlessly amplified by their coupling in a cyclic chain, resulting in such macroscopic motions at the electrode/solution interface. All of the phenomena can be explained on the basis of the modern theory proposed by Aogaki et al. for the polarographic streaming maxima of the first kind.     

Surface charging of layered double hydroxides during dynamic interactions of anions at the interfaces

In this research, we investigated the effect of dynamic anion adsorption/exchange on the surface charging property of Mg(2)AlClLDH and Mg(2)AlCO(3)LDH particles that show the average zeta potential of 41 and 34 mV in the as-prepared suspension, respectively. The addition of NaCl up to 3x10(-3) M in the suspension does not obviously affect the zeta potential of both LDHs, which can be attributed to the less affinity of Cl(-) to LDH. The introduction of Na(2)CO(3) severely reduces the zeta potential at the CO(3)(2-) concentration higher than 1x10(-4) M, and to the negative value in both LDH systems at ca. 2x10(-3) M, which is presumably resulted from the exchange and the re-orientation of CO(3)(2-) in a tilt/vertical style on the surface. All four organic anions (dodecyl sulfate, folate, citrate and polyacrylate) also significantly affect the zeta potential of the LDH particles. At the lower concentrations of organic anionic groups (<1x10(-4) M), the zeta potential was slightly affected, i.e. limited exchange/adsorption. However, the concentration increasing to some point suddenly decreases and reverses the zeta potential of the LDH particles, which is presumably caused by the hydrophobic interactions that bind the hydrophobic hydrocarbon chains (especially in dodecyl sulfate) into the micelle-like bilayer bunches on the LDH surface. In addition, the effect of pH in 5.5-11.0 on the LDH particle surface charging is mainly reflected through the conversion of CO(3)(2-) to HCO(3)(-)/H(2)CO(3) when pH decreases from ca. 11 to 6, with limited contribution from protonation/deprotonation and exchange/adsorption.     

Amphiphilic pyrimidinophane,a new dimeric surfactant: Synthesis,aggregation, and catalytic activity

Abstract Tensiometry, conductometry, dynamic light scattering, and potentiometry are used to study the aggregation of a new amphiphilic alkylated pyrimidinophane (APP) in aqueous solutions in the presence of polyethylen-imine. The new geminal surfactant is shown to possess high micellization ability (CMC = 0.00001 M) due to the presence of an additional alkyl radical in the pyrimidine fragment. APP aggregates are characterized by a low degree of counterion binding (lower than 50%). Spectrophotometry is employed to investigate the catalytic activities of individual surfactant solutions and solutions of APP—polyethylenimine binary mixtures with respect to the hydrolysis of phosphonic acid esters. The effect of APP on phosphonate hydrolysis is typical of cationic surfactants. The higher acceleration is observed for the hydrolysis of a more hydrophobic phophonate.     

Poly(3‐hexylthiophene) aggregation at solvent–solvent interfaces

The aggregation behavior of P3HT is investigated at the interface of orthogonal solvents for P3HT. The changeable characteristics of P3HT aggregate dispersions, for example, extent of aggregation and intrachain order, are studied by varying (1) the interfacial area, (2) the poor solvent used to induce aggregation – dichloromethane (DCM), hexane (HEX), and acetonitrile (AcN) – and (3) the relative composition of the good solvent, chloroform (CF), and poor solvents. The results are compared to those observed using rapid injection of the solvent. Miscibility gap values (Δδ) provide a reasonable justification of the assembly behavior of P3HT in the solvent mixtures in terms of the kinetics of polymer aggregation and the kinetics of solvent mixing at the interface. Atomic force microscopy (AFM) is used to analyze the morphology of films processed from dispersions with disparate characteristics, but having the same solvent composition, for example, 70:30 CF:HEX or 60:40 CF:DCM. Based on the disparity of the kinetics and miscibility gap values, the prevalence of specific structural motifs in the films, for example, spheroids (globules) and fibers, is effectively rationalized in terms of the structural attributes of the aggregates in the liquid phase rather than the evaporation rate (boiling point) differences of the solvents in the mixture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 999–1011     

In situ measurement of conformational changes in proteins at liquid interfaces by circular dichroism spectroscopy

A new circular dichroism (CD) spectroscopy technique for studying conformational changes in proteins in situ at the air-water interface is described. By using this technique, conformations of four proteins, viz., beta-casein, bovine serum albumin (BSA), lysozyme, and fibrinogen in the adsorbed state at the air-water interface have been studied. beta-Casein, which is predominantly in a disordered state in solution, assumes a beta-sheet conformation at the air-water interface. On the other hand, lysozyme and fibrinogen, which are alpha+beta-type proteins in solution, become beta-type proteins by completely transforming their alpha-helix structure into beta-sheets. Bovine serum albumin, which is an alpha-type protein in solution, loses its alpha-helix and becomes a disordered protein at the air-water interface. The results indicated that during unfolding and film formation at the interface, structural changes in proteins, regardless of their initial native state, follow the course of increasing beta-sheet and disordered structure and decreasing alpha-helix content. Although this seems to be the general trend, the exceptional case of BSA suggests, however, that this is not universal.     

Direct observation of layered structures at ionic liquid/solid interfaces by using frequency-modulation atomic force microscopy

Presence of inhomogeneous layered structures of ionic liquid (IL) molecules at IL/HOPG and IL/mica interfaces was directly detected and imaged by using frequency-modulation atomic force microscopy. High stability of the layered structures may disturb their interface applications to catalysis and electrochemistry.     

Nanoparticle assembly at fluid interfaces: structure and dynamics

The self-assembly of nanoparticles at fluid interfaces, driven by the reduction in interfacial energy, was investigated. With spherical, tri-n-octyl-phosphine-oxide covered cadmium selenide (CdSe) nanoparticles (1-8 nm), thermal fluctuations compete with the interfacial segregation giving rise to a size-dependent self-assembly of the particles. The structure of the nanoparticle assembly was studied using electron microscopy, atomic force microscopy, and X-ray scattering in situ, which indicate that the particles form a densely packed monolayer. The energetics of the adsorption of nanoparticles onto the interface was revealed by time-dependent fluorescence studies on a mixture of two different sized nanoparticles at the interface. The dynamics of the nanoparticles at the fluid interface, probed using fluorescence photobleaching methods, suggests a liquid-like behavior. The results have implications in the design of hierarchical self-assemblies of nanoparticles for the one-step fabrication of devices on multiple length scales.     

Amphiphilic diblock,triblock, and star block copolymers by living radical polymerization: Synthesis and aggregation behavior

Copper(I)‐mediated living radical polymerization was used to synthesize amphiphilic block copolymers of poly(n‐butyl methacrylate) [P(n‐BMA)] and poly[(2‐dimethylamino)ethyl methacrylate] (PDMAEMA). Functionalized bromo P(n‐BMA) macroinitiators were prepared from monofunctional, difunctional, and trifunctional initiators: 2‐bromo‐2‐methylpropionic acid 4‐methoxyphenyl ester, 1,4‐(2′‐bromo‐2′‐methyl‐propionate)benzene, and 1,3,5‐(2′‐bromo‐2′‐methylpropionato)benzene. The living nature of the polymerizations involved was investigated in each case, leading to narrow‐polydispersity polymers for which the number‐average molecular weight increased fairly linearly with time with good first‐order kinetics in the monomer. These macroinitiators were subsequently used for the polymerization of (2‐dimethylamino)ethyl methacrylate to obtain well‐defined [P(n‐BMA)_x‐b‐PDMAEMA_y]_z diblock (15,900; polydispersity index = 1.60), triblock (23,200; polydispersity index = 1.24), and star block copolymers (50,700; polydispersity index = 1.46). Amphiphilic block copolymers contained between 60 and 80 mol % hydrophilic PDMAEMA blocks to solubilize them in water. The polymers were quaternized with methyl iodide to render them even more hydrophilic. The aggregation behavior of these copolymers was investigated with fluorescence spectroscopy and dynamic light scattering. For blocks of similar comonomer compositions, the apparent critical aggregation concentration (cac = 3.22–7.13 × 10^?3 g L^?1) and the aggregate size (ca. 65 nm) were both dependent on the copolymer architecture. However, for the same copolymer structure, increasing the hydrophilic PDMAEMA block length had little effect on the cac but resulted in a change in the aggregate size. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 439–450, 2002; DOI 10.1002/pola.10122     

Fluorosurfactants at structural extremes: adsorption and aggregation

Fluorosurfactants with several structural modifications have been synthesized, and the air/water interface and bulk aggregation properties investigated. The compounds were fluorinated ethylene oxide (EO) nonionics where the number and position of the hydrophilic group(s) has been radically altered to generate linear, bolaform, and Y-shaped analogues. A noticeable structure-interfacial packing relationship was observed via both tensiometric measurements and neutron reflection studies: the limiting molecular areas, a(cmc), and surface excesses, gamma(cmc), are strongly dependent on the number and position of the EO headgroups. Differing bulk aqueous properties were also observed. Small-angle neutron scattering shows an evolution of micelle structure from cylindrical to disk-like aggregates on changing from Y-shaped to bolaform molecular structure.     

Theory of incomplete crystals,surfaces, defects,interfaces and layered structures

This paper presents systematically the surface Green function matching analysis for systems with inherently discrete structure - e.g. phonons or tight-binding electrons. The general interface problem, the free surface, the vacancy - as a particular case of an inner surface - and point defects and adsorbates - as examples of interfaces - can all be treated on the same footing. By combining ideas of scattering and matching a unified approach encompasses a variety of different problems while yielding a method which can be used in practice for calculating e.g. surface, interface or defect state eigenvalues or spectral functions of interest. This holds for any type of physical states - electrons, phonons, waves - and for any chosen model. The practical combination with transfer matrix algorithms for planar geometry is discussed and an algorithm for growing shells is presented for point defects. Phonons allow for a discussion of the long-wave limit and contract is thus established with the surface Green function matching analysis for continuous media. The analysis is extended to layered structures - quantum wells and superlaticces - both for discrete and continuous systems.     

Hydrophobins: Proteins that self assemble at interfaces

Hydrophobins are surface active proteins that are produced by filamentous fungi. They are interesting from a Surf Sci point of view because some of their properties as surface active proteins are quite spectacular. In this review, recent advances in understanding these properties will be surveyed. We will attempt to define what the properties are that make them unique. As an understanding of both structure and function of hydrophobins is emerging we see that this is paving the way for industrial applications as well as an understanding of their biological functions.

Major recent advances

Recently there has been a clear increase in attempts to use hydrophobins in applications. We are starting to understand their unique properties as surfactants and especially applications related to the stability and development of foams and various surface treatments are emerging. There are several new reports on molecular structures as well on mechanisms of self-assembly. Hydrophobins have functions in biology that are far from understood, but also here techniques are developing and a broader understanding is emerging.     

Water structure at interfaces: the present situation

This paper discusses the structure of adsorbed water at interfaces. It begins with a review of the development of the research, then examines and compares some of the most important models in this field. The results of recent spectroscopic work, especially those of IR spectroscopy, are discussed and applied to the selection of the most probable model.     

Effect of organic solvents on J aggregation of pseudoisocyanine dye at mica/water interfaces: morphological transition from three-dimension to two-dimension

Morphological and spectroscopic properties of pseudoisocyanine (PIC) J aggregates produced at mica/solution interfaces have been characterized by absorption/fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. Addition of organic solvents (1-propanol (PrOH) or 1,4-dioxane (Dox)) into aqueous solutions of the PIC dye induced a transition of the morphology of the interfacial J aggregates. The characteristic feature of this transition is the thickness (or height) change of the aggregate domain layers from three-dimensions to two-dimensions: The domain area of the J aggregates was dependent on the amount of the organic cosolvent, while the domain thickness was dependent on the type of the cosolvent. In pure aqueous solution, the J aggregates at the mica/water interface had a three-dimensional structure with the height of approximately 3 nm (multilayer structure). In mixed solvents of PrOH/water or Dox/water (5 or 10 vol%), the interfacial aggregates became a bilayer or monolayer structure, respectively, assuming that PIC molecules are adsorbed on their molecular plane perpendicular to the mica surface. Meanwhile, optical properties (band width and peak position) of the J band were invariant upon addition of the organic cosolvents, suggesting that molecular packing in the J aggregates is essentially unchanged. These results revealed that spectroscopic properties of the interfacial PIC J aggregates were determined only by the lateral (two-dimensional) interaction within the adsorbed monolayer of PIC molecules on mica, and interlayer interaction in the multilayered J aggregate was consequently small.